CN101283005A - Composition curable with actinic energy ray - Google Patents

Composition curable with actinic energy ray Download PDF

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Publication number
CN101283005A
CN101283005A CNA2006800370958A CN200680037095A CN101283005A CN 101283005 A CN101283005 A CN 101283005A CN A2006800370958 A CNA2006800370958 A CN A2006800370958A CN 200680037095 A CN200680037095 A CN 200680037095A CN 101283005 A CN101283005 A CN 101283005A
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composition
methyl
acrylate
acid
pattern
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长谷川三高
谷内健太郎
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Toagosei Co Ltd
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Toagosei Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

An actinic-energy-ray-curable composition which, when used as an actinic-energy-ray-curable composition for pattern formation, has high sensitivity to exposure light and satisfactory developability and can form a fine and accurate pattern. After cure, the pattern is excellent in various properties including coating film strength, heat resistance, and chemical resistance. Also provided is a method of forming a pattern. The composition comprises as essential ingredients (a) a compound which is an adduct of a hydroxylated compound having three or more (meth)acryloyl groups with an acid anhydride and (b) an acid anhydride or/and a hydrolyzate of an acid anhydride, wherein the ingredient (b) is contained in an amount of 0.1-20 parts by mass per 100 parts by mass of the ingredient (a). The method comprises applying the composition to a substrate to form a coating film, subsequently irradiating the film with actinic energy rays through a mask having a specific pattern and placed over the film to thereby cure it, and removing uncured parts with a developing liquid.

Description

Active energy ray-curable composition
Technical field
The present invention relates to a kind of active energy ray-curable composition, composition of the present invention can be used for patterns such as printing ink, coating and photoresist material and form the various uses of using composition, particularly because the alkali-developable excellence, therefore can be preferably used as pattern formation and use composition, belong to these technical fields.
Background technology
At present, the chromatic filter that uses during liquid crystal panel is made uses the chromatic filter that has formed pixels such as red, green, blue with methods such as staining, print process, electrodip process and colo(u)rant dispersion methods on glass substrate usually.
In existing chromatic filter, the chromatic filter that utilizes staining to form is to use the photoresist that is mixed with in gelatin or polyvinyl alcohol etc. as the dichromate of sensitizer to form to dye behind the image to be made.There are the following problems to utilize the situation of this staining: owing to form pleochroic image on same substrate, therefore need resist printing operation, complex procedures.But also there are the following problems: owing to use dyestuff, therefore, except the photostabilization difference, as the dichromate that sensitizer is used, consider from the viewpoint that prevents public hazards, preferably do not use.
The chromatic filter that utilizes print process to form makes thermo-cured ink or light-curable ink be needed on glass substrate with methods such as silk screen printing or aniline printings and makes.If print process, owing to do not need image to form, dye, so operation is simple and easy, but then, can not obtain high meticulous image, and problem is also being arranged aspect the smoothness of printing ink.
The chromatic filter that utilizes electrodip process to form flood the glass substrate that is provided with electrode in the bath that contains pigment or dyestuff, utilize electrophoresis to move adheres to color to make.The chromatic filter smoothness excellence of utilizing electrodip process to form, but owing to need on glass substrate, to be provided with in advance electrode, therefore exist to be difficult to form the such problem of complicated patterns.
On the other hand, the chromatic filter that utilizes the colo(u)rant dispersion method to form is to make by utilizing the painted photoresist material that is dispersed with pigment in the photocurable compound to form image.The colo(u)rant dispersion method has following advantage: can make the chromatic filter of high heat resistance, in addition, not need dyeing, and, can form high-precision image.
Therefore, at present the colo(u)rant dispersion method becomes the main flow of chromatic filter manufacturing technology, but in the colo(u)rant dispersion method, and the painted photoresist material that contains a large amount of pigment in utilization carries out image when forming, and has on substrate the such problem of pigment residue (residue adheres to) easily.In the manufacturing of chromatic filter, owing to form red, green, blue pixels successively, therefore, the reason of adhering to color reprodubility that can become chromatic filter and the deteriorations such as smoothness of filming of residue.
In order to prevent that this residue from adhering to, carrying out the control development time at present, regulating solution level and utilizing brush etc. to remove the method for residue etc.
In addition, as the method beyond above-mentioned, also motion has the method (patent documentation 1,2) of adding organic carboxyl acid in painted photoresist material, improves deliquescent method or be that organic carboxyl acid acid anhydride below 800 makes an addition to the method (patent documentation 3) in the painted photoresist material with molecular weight by the acid number that improves adhesive resin.
Patent documentation 1: the spy opens flat 4-369653 communique
Patent documentation 2: the spy opens flat 5-343631 communique
Patent documentation 3: the spy opens flat 8-292316 communique
Summary of the invention
But, above-mentioned control development time, regulate solution level and utilize brush etc. to remove the method for residue, can not remove fully and residue takes place adhere to, and, have also that operability reduces, cost rises and the problems such as liquid waste disposal of developing solution.
In addition, add the method for organic carboxyl acid and improve the method for the acid number of adhesive resin, the method for adding acid anhydrides, when reducing the compounding ratio of adhesive resin, can not prevent residue fully and adhere to.
The objective of the invention is to, a kind of active energy ray-curable composition or pattern formation method are provided, described active energy ray-curable composition is when using composition as the formation of active energy ray-curable pattern, exposure sensitivity height, development are good, can form precision, pattern accurately, and after curing, various physical properties excellent such as coating strength, thermotolerance and resistance to chemical reagents.And, be to provide a kind of active energy ray-curable coloured composition or pattern formation method, when described active energy ray-curable coloured composition is made at the chromatic filter that is used for the liquid crystal panel manufacturing, except above-mentioned performance, can also when forming the pixel of chromatic filter, reduce the residue of pigmented layer.
Below, the present invention is at length described.In addition, in this manual, (methyl) vinylformic acid is meant vinylformic acid and/or methacrylic acid, and (methyl) acrylate is meant acrylate and/or methacrylic ester, and (methyl) acryl is meant acryl and/or methacryloyl.
The present invention relates to a kind of active energy ray-curable composition; its be contain compound (a) [below be called " (a) composition "] and, the hydrolyzate (b) of acid anhydrides or acid anhydrides [below be called " (b) composition "] is as composition that must composition; described compound (a) is that the addition acid anhydrides forms on the compound with (methyl) acryl and hydroxyl more than 3; with respect to (a) composition 100 mass parts, contain (b) composition with the ratio of 0.1～20 mass parts.
Below, (a) composition, (b) composition and other compositions are described.
1. (a) composition
(a) composition is the compound that addition has acid anhydrides in the compound with (methyl) acryl and hydroxyl more than 3 (below be called " multifunctional (methyl) crylic acid hydroxy ester ").
Multifunctional (methyl) crylic acid hydroxy ester can be enumerated particularly: ditrimethylolpropane three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate and Dipentaerythritol five (methyl) acrylate etc.
Multifunctional (methyl) crylic acid hydroxy ester among the present invention can contain the by product that generates in the manufacturing process, promptly not have a compound with (methyl) acryl more than 4 of hydroxyl.Can enumerate for example tetramethylolmethane four (methyl) acrylate and Dipentaerythritol six (methyl) acrylate etc.These contain tetramethylolmethane three (methyl) acrylate usually in tetramethylolmethane four (methyl) acrylate, contain Dipentaerythritol five (methyl) acrylate in Dipentaerythritol six (methyl) acrylate.
These do not have the compound with (methyl) acryl more than 4 of hydroxyl, can the ratio with 20～80 quality % contain in multifunctional (methyl) crylic acid hydroxy ester composition.
The manufacture method of multifunctional crylic acid hydroxy ester can be enumerated: in the presence of an acidic catalyst, with (methyl) vinylformic acid with alcohol heats, stirring method etc.An acidic catalyst can be enumerated: sulfuric acid, tosic acid and methylsulfonic acid etc.In addition, temperature of reaction is preferably 70 ℃～140 ℃ as long as suitably set according to compound that uses and purpose.When this temperature of reaction is lower than 70 ℃, react slack-off, on the other hand, when temperature of reaction surpassed 140 ℃, reaction system became unstable sometimes, generates impurity or gelation takes place.
When this reacted, the low organic solvent of solubleness of the water that generates in preferred use and the esterification made the water azeotropic promote dehydration simultaneously.Preferred organic for example can be enumerated: aromatic hydrocarbonss such as toluene, benzene and dimethylbenzene; Aliphatic hydrocarbon such as hexane and heptane; And ketone such as butanone and pimelinketone etc.In addition, organic solvent can be removed by underpressure distillation after reaction, when having used the solvent of the problem that is destitute of smell, in order to adjust the viscosity of composition, can not distill and remove and directly use.
Can enumerate particularly as the alcohol in the above-mentioned reaction: oxirane affixture of polyvalent alcohol such as ditrimethylolpropane, tetramethylolmethane and Dipentaerythritol and these polyvalent alcohols etc.Above-mentioned oxirane can be enumerated oxyethane and propylene oxide etc.
In addition, (methyl) acrylic ester polymerization in order to prevent to obtain can add stopper in reaction solution.This stopper for example can be enumerated: Resorcinol, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol and thiodiphenylamine etc.
(a) composition can synthesize by the reaction of above-mentioned multifunctional (methyl) crylic acid hydroxy ester and acid anhydrides.
Acid anhydrides can be enumerated: succinyl oxide, the 1-dodecenyl succinic anhydride, maleic anhydride, Pyroglutaric acid, itaconic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, first bridge Tetra Hydro Phthalic Anhydride, methyl first bridge Tetra Hydro Phthalic Anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride and trimellitic acid 1,2-anhydride are equal to the compound that has 1 anhydride group in a part; And pyromellitic dianhydride, Tetra hydro Phthalic anhydride dipolymer, phenyl ether tetracarboxylic dianhydride, diphenylsulfone acid's dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic acid dianhydride, phenyl ether tetracarboxylic anhydride and trimellitic acid 1,2-anhydride glycol ester (commercially available product has for example new Japanese physics and chemistry (strain) system, trade(brand)name リ カ シ ッ De TMEG-100) are equal to the compound that has 2 anhydride group in a part.
Wherein, the compound of preferred same intramolecularly with 1 anhydride group.
(a) as long as manufacture method of composition is according to ordinary method.
For example can enumerate, in the presence of catalyzer, under 60～110 ℃, make multifunctional (methyl) crylic acid hydroxy ester and 1～20 hour method of anhydride reaction etc.
The catalyzer of this moment can be enumerated: N, N-dimethyl benzylamine, triethylamine, Tributylamine, triethylenediamine, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium bromide, 4 bromide, cetyl trimethylammonium bromide and zinc oxide etc.
(a) ratio in the composition of composition preferably accounts for 10～80 quality % as long as suitably select according to purpose and purposes in composition.
2. (b) composition
(b) composition is the hydrolyzate of acid anhydrides or acid anhydrides.
(b) acid anhydrides in the composition can be enumerated and the identical compound of enumerating as the raw material of above-mentioned (a) composition of acid anhydrides.The hydrolyzate of acid anhydrides can be enumerated the dicarboxylic acid that acid anhydrides forms by hydrolysis.
(b) acid anhydrides in the composition, the acid anhydrides that uses during with synthetic (a) composition can be identical compound, also can be different compounds.
In addition, (b) composition can directly use the compound that unreacted acid anhydrides generation hydrolysis forms in when synthetic (a) composition unreacted acid anhydrides or the reaction, also can carry out compounding separately again in addition.
(b) components in proportions is 0.1～20 mass parts with respect to (a) composition 100 mass parts, is preferably 0.1～10 mass parts.When (b) components in proportions is lower than 0.1 mass parts, the development deficiency, and residue adheres to increase.In addition, when it surpassed 20 mass parts, pigment-dispersing reduced or the stability of dispersion liquid reduces.
At this, content (a) preferably use typical curve to efficient liquid phase chromatographic analysis, use anti-phase silica column and make the elutriant of water/methyl alcohol class measure the value that obtains and the area that obtains is proofreaied and correct.The condition determination of this moment can be listed below.
[efficient liquid phase chromatographic analysis condition]
Device: East ソ one (strain) system SC-8010
Post: East ソ one (strain) system ODS-100z
Anti-phase (ODS) post (internal diameter 4.6mm, length 250mm).Fill anti-phase (ODS) silicon dioxide granule of particle diameter 5 μ m.
The solution 5 μ l that are dissolved with the 100mg composition in the 10ml solvent are supplied with above-mentioned post.
Analysis temperature: 40 ℃
Elutriant: 0.015% phosphoric acid water: methyl alcohol (volume ratio)=45: 55 (initially) → 30: 70 (30min) → 0: 100 (45-50min)
The flow velocity of elutriant: 1.0ml/min
Detect wavelength: UV 210nm
Secondly, content (b) preferably use typical curve to the ion chromatograph analysis, use anion-exchange column and use carbonic acid class elutriant to measure and the area that obtains is proofreaied and correct and the value that obtains.The condition determination of this moment can be listed below.
[ion chromatograph assay determination condition]
Device: DIONEX (strain) system DIONEX DX-300
Separator column: DIONEX (strain) makes IonPacAS4A-SC (with ethylene vinyl benzene-Vinylstyrene analog copolymer is base material, is the anion-exchange column of ion-exchange group with the alkanol quaternary amine)
Guard column: DIONEX (strain) makes IonPacAG4A-SC (with ethylene vinyl benzene-Vinylstyrene analog copolymer is base material, is the anion-exchange column of ion-exchange group with the alkanol quaternary amine)
Elutriant: 1.8mM-Na 2CO 3/ 1.7mM-NaHCO 3
Flow: 1.5ml/min
Suppressor: ASRS-ULTRA-II (egr mode, current value 50mA)
Detector: specific conductivity
Sample injection rate: 50 μ L
Program: after the dilution with toluene of sample, add the water of 5 times of amounts of sample, after vibrate 10 minutes and leaving standstill, divide and take off layer (water layer), make working sample with 10 times of amounts.
In addition, (b) composition is the situation of acid anhydrides, also exists in the acid anhydrides that has carried out partial hydrolysis in the ion chromatography, and is as long as hold the total amount as the hydrolyzate of acid anhydrides and acid anhydrides, just out of question in the present invention.
3. other compositions
Composition of the present invention is other compositions of compounding as required.
Specifically, can compounding Photoepolymerizationinitiater initiater, organic solvent, contain unsaturated group compound, alkali soluble resin, pigment, dyestuff, defoamer, flow agent, mineral filler and organic filler etc.In addition, can add antioxidant, photostabilizer, UV light absorber and stopper etc. on a small quantity as required.
Below, to Photoepolymerizationinitiater initiater, organic solvent, contain the unsaturated group compound and alkali soluble resin at length describes.
3-1. Photoepolymerizationinitiater initiater
Composition of the present invention is cured by the irradiation active energy ray, and the active energy ray of this moment can be enumerated: electron rays, visible rays and ultraviolet ray etc.Wherein, visible rays or ultraviolet ray be not because of needing special device and easy to be preferred.
When being set at visible rays or ultra-violet solidified composition, compounding Photoepolymerizationinitiater initiater in composition.In addition, when being set at the electron(beam)curing composition, not necessarily need the compounding Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater [below be called " (c) composition "] for example can be enumerated: bisglyoxaline compounds, benzoin compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, thioxanthone compounds, compound in triazine class and ketals etc.
The concrete example of bisglyoxaline compounds can be enumerated: 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four (4-oxyethyl group carbonyl phenyls)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-oxyethyl group carbonyl phenyls)-1,2 '-bisglyoxaline, 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline and 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
When using the bisglyoxaline compounds as (c) composition, can further improve aspect the sensitivity preferred and give and body with hydrogen.This said " hydrogen is given and body ", be to point to by the free radical of exposure by the generation of bisglyoxaline compounds, can supply with the compound of hydrogen atom.
Hydrogen is given to give with the preferred mercaptan hydrogen-like of body and is given with body etc. with body and amine hydrogen.
The mercaptan hydrogen-like give with body comprise with phenyl ring or heterocycle be parent nucleus, have more than 1, preferred 1～3, further preferred 1～2 compound that is bonded directly to the sulfydryl of this parent nucleus.The mercaptan hydrogen-like can be enumerated with the concrete example of body: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles and 2-sulfydryl-2,5-Dimethylamino pyridine etc.These mercaptan hydrogen-likes give with body in, preferred 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.
Amine hydrogen give with body comprise with phenyl ring or heterocycle be parent nucleus, have more than 1, preferred 1～3, further preferred 1～2 compound that is bonded directly to the amino of this parent nucleus.Amine hydrogen can be enumerated with the concrete example of body: 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylin) benzophenone, 4-diethylin methyl phenyl ketone, 4-dimethylamino Propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylaminobenzoic acid and 4-dimethylamino benzonitrile etc.
Hydrogen is given and can be used separately with body or mix use more than 2 kinds, be used in combination mercaptan hydrogen-like more than a kind and give with body and the amine hydrogen more than a kind and give and body, when the spacer that forms or pixel are developed, be difficult for from substrate come off and the intensity of spacer or pixel and sensitivity preferred aspect also high.In addition, also can preferably use the hydrogen that has sulfydryl and amino simultaneously to give and body.
The concrete example of benzoin compounds can be enumerated: benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin ethyl isobutyl ether and 2-benzoyl methyl benzoate etc.
The concrete example of acetophenone compounds can be enumerated: 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-methyl thio-phenyl)-2-methyl-2-morpholino propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methyl-2-hydroxy propane-1-ketone, 1-(4-morpholino phenyl)-2-benzyl-2-dimethylamino butane-1-ketone, 1-hydroxycyclohexylphenylketone and 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.
The concrete example of benzophenone compound can be enumerated: benzyl dimethyl ketal, benzophenone, 4,4 '-two (dimethyl benzophenones) and 4,4 '-two (diethyl benzophenone) etc.
The concrete example of α-cyclohexadione compounds can be enumerated: dimethyl diketone, dibenzoyl, methyl benzoylformate etc.
The concrete example of multinuclear quinones can be enumerated: anthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone and 1,4-naphthoquinones etc.
The concrete example of xanthone compounds can be enumerated: xanthone, thioxanthone, 2-clopenthixal ketone etc.
The concrete example of compound in triazine class can be enumerated: 1,3,5-three (trichloromethyl)-s-triazine, 1,3-two (trichloromethyl)-5-(2 '-chloro-phenyl-)-s-triazine, 1,3-two (trichloromethyl)-5-(4 '-chloro-phenyl-)-s-triazine, 1,3-two (trichloromethyl)-5-(2 '-p-methoxy-phenyl)-s-triazine, 1,3-two (trichloromethyl)-5-(4 '-p-methoxy-phenyl)-s-triazine, 2-methyl-4,6-two (trichloromethyl)-s-triazine, 2-(4 '-p-methoxy-phenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-phenetole vinyl)-4,6-two (trichloromethyl)-s-triazine and 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazine etc.
Wherein, because 1-hydroxycyclohexylphenylketone and 1-(4-methyl thio-phenyl)-2-methyl-2-morpholino propane-a small amount of use of 1-ketone can cause and promote polyreaction by the irradiation active energy ray, therefore, preferably use in the present invention.
(c) composition can use separately or also use more than 2 kinds.
(c) the compounding ratio of composition is with respect to solids component 100 mass parts beyond the Photoepolymerizationinitiater initiater in the composition, preferred 0.5～20 mass parts.When it was lower than 0.5 mass parts, light solidified was insufficient sometimes, and on the other hand, when it surpassed 20 mass parts, exposed portion was destroyed easily when alkali develops sometimes.And, can obtain aspect the high pattern of precision, (c) more preferably 2～10 quality % of components in proportions.
3-2. organic solvent
In the present invention, for the purposes such as coating of improved composition, can the compounding organic solvent.
Organic solvent [below be called " (d) composition "] is not as long as react with each composition of composition.And the rate of drying of filming suitable situation that obtain excellent from coating considers preferably have the organic solvent of 80～200 ℃ boiling point, wherein, more preferably has the organic solvent of 100～170 ℃ boiling point.
Specifically, for example can enumerate: aromatics such as toluene and dimethylbenzene; Fatty acid esters such as butylacetate, jasmal, propylene glycol monomethyl ether acetic ester and ethoxyethyl propionate; Cellosolve such as ethyl cellosolve and ethylene glycol butyl ether; Alkylene glycol ethers such as propylene glycol monomethyl ether; Alcohol such as ethanol, ethylene glycol and Diethylene Glycol; Ethers such as diethylene glycol dimethyl ether; Ketone such as methyl iso-butyl ketone (MIBK) and pimelinketone; N, methane amides such as dinethylformamide; Lactan such as butyrolactam and N-N-methyl-2-2-pyrrolidone N-; And lactone such as gamma-butyrolactone etc.
(d) composition can use separately or also use more than 2 kinds.
(d) preferably to reach the solid component concentration of composition be the ratio of 10～50 quality % to the compounding ratio of composition.
3-3. contain the unsaturated group compound
In composition of the present invention, contain unsaturated group compound [below be called " (e) composition "] beyond compounding as required (a) composition.
(e) composition for example can be enumerated: (methyl) vinylformic acid phenoxy ethyl; (methyl) ethoxy ethoxyethylacrylate; N-vinyl caprolactone; acryloyl morpholine; (methyl) glycidyl acrylate; (methyl) 2-Hydroxy ethyl acrylate; (methyl) vinylformic acid-2-hydroxy propyl ester; 1; 4-butyleneglycol one (methyl) acrylate; 1; 6-hexylene glycol two (methyl) acrylate; the nonanediol diacrylate; polyoxyethylene glycol two (methyl) acrylate; (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester; (methyl) vinylformic acid tribromophenyl; 2; 2-two (4-(methyl) acryloxy ethoxyl phenenyl)-propane; 2; 2-two (4-(methyl) acryloxy diethoxy phenyl)-propane; 2,2-two (4-(methyl) acryloxy triethoxy phenyl)-propane; ethylene glycol bisthioglycolate (methyl) acrylate; (methyl) vinylformic acid tribromo phenyl oxygen base ethyl ester; trimethylolpropane tris (methyl) acrylate; four (methyl) vinylformic acid pentaerythritol ester; two (methyl) acrylate of bisphenol A type epoxy resin; poly-(methyl) acrylate of various polyurethane polyureas (methyl) acrylate and polyester etc.
(e) the preferred compounding ratio of composition is the scope of 0～50 quality % in composition.
3-4. alkali soluble resin
Alkali soluble resin among the present invention [below be called " (f) composition "] as long as work as tackiness agent with respect to (f) composition, to the developing solution that uses in the development treatment operation, especially preferably alkaline developer is had solubility, just is not particularly limited.
(f) composition can be enumerated addition polymer, polyester, Resins, epoxy and polyethers etc., preferably the addition polymer that the ethylenically unsaturated monomer polymerization is obtained.
(f) composition preferably has the alkali soluble resin of carboxyl, especially preferably have 1 above carboxyl ethylenically unsaturated monomer (below be called " containing the carboxyl unsaturated monomer ") and can with the multipolymer of the ethylenically unsaturated monomer of its copolymerization (below be called " copolymerization unsaturated monomer ") (below be called " carboxy-containing copolymer ").
The example that contains the carboxyl unsaturated monomer can be enumerated: unsaturated monocarboxylic acid classes such as (methyl) vinylformic acid, butenoic acid, α-Lv Bingxisuan and styracin; Unsaturated dicarboxylic acid or its acid anhydride classes such as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride and methylfumaric acid; Unsaturated polycarboxylic acid more than 3 yuan or its acid anhydride class; One [(methyl) acryloxyalkyl] ester class of polycarboxylic acids more than 2 yuan such as succsinic acid one (2-(methyl) acryloxy ethyl) ester and phthalic acid one (2-(methyl) acryloxy ethyl) ester; And ω-two ends such as carboxyl polycaprolactone one (methyl) acrylate have one (methyl) esters of acrylic acid etc. of the polymkeric substance of carboxyl and hydroxyl.Contain in the carboxyl unsaturated monomer at these, ω-carboxyl polycaprolactone one acrylate and phthalic acid one (2-acryloxy ethyl) ester is respectively with ア ロ ニ Star Network ス M-5300 and M-5400[East Asia synthetic (strain)] trade(brand)name sell.
Contain that the carboxyl unsaturated monomer can use separately or mix more than 2 kinds and use.
In addition; as the copolymerization unsaturated monomer; so long as get final product with containing the monomer that the carboxyl unsaturated monomer carries out copolymerization, optimization aromatic vinyl compound, unsaturated carboxylate type, unsaturated acid imide and end have the macromonomer class of one (methyl) acryl etc.
Aromatic ethenyl compound can be enumerated: vinylbenzene, alpha-methyl styrene, adjacent Vinyl toluene, a Vinyl toluene, to Vinyl toluene, to chloro-styrene, O-methoxy vinylbenzene, meta-methoxy vinylbenzene, to methoxy styrene, 2-vinyl benzyl methyl ether, 3-vinyl benzyl methyl ether, 4-vinyl benzyl methyl ether, 2-vinyl benzyl glycidyl ether, 3-vinyl benzyl glycidyl ether and 4-vinyl benzyl glycidyl ether etc.
Unsaturated carboxylate type can be enumerated: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-3-hydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid-2-methoxyl group ethyl ester, (methyl) vinylformic acid-2-phenoxy ethyl, methoxyl group Diethylene Glycol (methyl) acrylate, methoxyl group triethylene glycol (methyl) acrylate, MPEG (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, (methyl) isobornyl acrylate, three ring [5.2.1.0 2.6] decane-8-base (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester and glycerine one (methyl) acrylate etc.
Unsaturated acid imide can be enumerated: maleimide, N-phenylmaleimide and N-cyclohexyl maleimide etc.
The macromonomer class that end has one (methyl) acryl can enumerate have polystyrene, the macromonomer class of polymer molecular chains such as poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and polysiloxane etc.
As the copolymerization unsaturated monomer, except that above-mentioned, also can enumerate: 2-(3,4,5,6-tetrahydric phthalimide) imide (methyl) esters of acrylic acid such as ethyl (methyl) acrylate, 2-(2,3-dimethyl maleimide) ethyl (methyl) acrylate; (methyl) vinylformic acid-2-amino ethyl ester, (methyl) vinylformic acid-2-dimethylaminoethyl, the amino propyl ester of (methyl) vinylformic acid-2-, vinylformic acid-2-dimethylamino propyl ester, the amino propyl ester of (methyl) vinylformic acid-3-and (methyl) vinylformic acid-unsaturated carboxylic acid aminoalkyl ester classes such as 3-dimethylamino propyl ester; Unsaturated carboxylic acid glycidyl ester classes such as (methyl) glycidyl acrylate; Indenes classes such as indenes and 1-methyl indenes; Vinyl carboxylates classes such as vinyl-acetic ester, propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as methoxy ethylene, ethyl vinyl ether and glycidyl allyl ether; Acrylonitrile compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing and vinylidene dicyanide; Unsaturated acyl amines such as (methyl) acrylamide, α-propenyl chloride acid amides and N-2-hydroxyethyl (methyl) acrylamide; And aliphatics conjugated dienes such as 1,3-butadiene, isoprene and chloroprene etc.
These copolymerization unsaturated monomers can use separately or mix more than 2 kinds and use.
Carboxy-containing copolymer is necessary composition with (methyl) vinylformic acid, preferably according to circumstances also contains to be selected from succsinic acid one (2-(methyl) acryloxy ethyl) ester, the containing carboxyl unsaturated monomer composition and be selected from vinylbenzene of at least a kind of compound in ω-carboxyl polycaprolactone one (methyl) acrylate, (methyl) methyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, glycerine one (methyl) acrylate, N-phenylmaleimide, at least a kind multipolymer in polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer (below be called " carboxy-containing copolymer (α) ".)。
The concrete example of carboxy-containing copolymer (α) can be enumerated: (methyl) vinylformic acid/(methyl) methyl acrylate copolymer, (methyl) vinylformic acid/(methyl) benzyl acrylate multipolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate multipolymer, (methyl) vinylformic acid/(methyl) glycidyl acrylate multipolymer, (methyl) vinylformic acid/(methyl) glycidyl acrylate/styrol copolymer, (methyl) vinylformic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer, (methyl) vinylformic acid/(methyl) methyl acrylate/polymethylmethacrylate macromonomer multipolymer, (methyl) vinylformic acid/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer, (methyl) vinylformic acid/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer, (methyl) vinylformic acid/(methyl) 2-Hydroxy ethyl acrylate/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/vinylbenzene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/succsinic acid one (2-(methyl) acryloxy ethyl) ester/vinylbenzene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/succsinic acid one (2-(methyl) acryloxy ethyl) ester/vinylbenzene/(methyl) allyl acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/vinylbenzene/(methyl) benzyl acrylate/glycerine one (methyl) acrylate/N-phenylmaleimide multipolymer, (methyl) vinylformic acid/ω-carboxyl polycaprolactone one (methyl) acrylate/vinylbenzene/(methyl) benzyl acrylate/glycerine one (methyl) acrylate/N-phenylmaleimide multipolymer etc.
The copolymerization ratio that contains the carboxyl unsaturated monomer in the carboxy-containing copolymer is generally 5～50 quality %, is preferably 10～40 quality %.At this moment, when above-mentioned copolymerization ratio is lower than 5 quality %, the composition that existence obtains is to the tendency of the solvability reduction of alkaline developer, on the other hand, when it surpasses 50 quality %, have following tendency: the solvability to alkaline developer is excessive, when utilizing alkaline developer to develop, cause easily spacer layer or pixel from substrate come off or the film on spacer surface coarse.
As (f) composition among the present invention, the cross-linking density of the cured film that the alkali soluble resin that has ethylenically unsaturated group on the side chain obtains in raising and improve excellence aspect coating strength, thermotolerance and the resistance to chemical reagents, therefore preferred.
The alkali soluble resin that has ethylenically unsaturated group on the side chain preferably has the alkali soluble resin of carboxyl.This resin can be set forth in addition in the above-mentioned carboxy-containing copolymer resin of unsaturated compound with epoxy group(ing) (below be called " epoxies unsaturated compound ") etc.
The epoxies unsaturated compound can be enumerated: (methyl) glycidyl acrylate and (methyl) acrylate of containing cyclohexene oxide etc. contain epoxy group(ing) (methyl) acrylate etc.
As long as the method for addition reaction is according to ordinary method, can by under organic solvent or solvent-free situation on carboxy-containing copolymer addition epoxies unsaturated compound make.The condition of addition reaction can be reacted suitable selective reaction temperature, reaction times and catalyzer according to each.
(f) weight-average molecular weight of composition (below be called " Mw ".) be generally 3,000～300,000, be preferably 5,000～100,000.In addition, number-average molecular weight (below be called " Mn ".) be generally 3,000～60,000, be preferably 5,000～25,000.
In addition, in the present invention, Mw and Mn are meant (GPC, eluting solvent: tetrahydrofuran (THF)) molecular weight of Ce Dinging carries out the value of polystyrene conversion with gel permeation chromatography.
In the present invention, have this specific Mw and (e) composition of Mn by use, can obtain the photosensitive polymer combination of development property excellence, can form pattern thus with clear pattern profile, and when developing on the substrate of unexposed portion and to be not easy to produce residue, scum, film on the light shield layer residual etc.In addition, (e) ratio (Mw/Mn) of the Mw of composition and Mn is generally 1～5, is preferably 1～4.
(f) composition can use separately or also use more than 2 kinds.
Compounding (a) composition or (e) situation of composition, (a) composition and (e) composition [below these being generically and collectively referred to as (methyl) acrylate composition] and (f) components in proportions, reaching (f) with (methyl) acrylate composition, the total amount of composition is a standard, preferably (f) composition is 10～90 quality %, more preferably 30～80 quality %.When (f) components in proportions surpasses 90 quality %, there is the tendency that reduces coating strength, thermotolerance, resistance to chemical reagents reduction because of cross-linking density.
(methyl) acrylate composition reaches (f) ratio of total amount in composition of composition, preferably is 10～50 quality % in composition.When this ratio was lower than 10 quality %, the thickness after the preceding baking was thin excessively, and on the other hand, when it surpassed 50 quality %, the viscosity of composition was too high, and coating is bad, or the thickness after the preceding baking is blocked up.
4. purposes
Composition of the present invention can be used for various uses.For example can enumerate that pattern such as photoresist material forms with coated materials such as composition, printing ink and coating etc.
In these purposes, composition of the present invention can be preferably used as pattern formation composition because of alkali-developable is excellent.
Because the exposure sensitivity height of composition of the present invention, development are very excellent, can form precision, pattern accurately, therefore, can be preferably used as pattern and form and use composition.
Composition of the present invention is being formed when use composition as pattern, preferably including (a) and (b), (c), (d) and reach (f) composition of composition.
Use the pattern formation method of said composition, as long as according to ordinary method, can enumerate: make composition coating on the substrate, dry and form film after, from it across mask irradiation active energy ray and it is solidified, utilize method that developing solution develops uncured portion etc. with specific pattern form.
Substrate can be enumerated glass and plastics etc.The preferred bases developing solution of developing solution, concrete example as hereinafter described.
Pattern forms can be enumerated with composition: be used to form photoresist materials such as etching photoresist and scolding tin photoresist material, liquid crystal panel in making column spacer, the pixel in the chromatic filter and deceive the coloured composition of matrix etc. and chromatic filter protective membrane etc.
For composition of the present invention, in these purposes, can be preferably as be used to form liquid crystal panel in making pixel and the coloured composition of black matrix etc. use.
4-1. coloured composition
When composition of the present invention is used as coloured composition, further compounding pigment and pigment dispersing agent.Below, these compositions are described.
Pigment is not particularly limited, and can use various organic or inorganic pigment.
The concrete example of pigment dyestuff can be enumerated: at Colour Index (C.I.; The Society ofDyers and Colourists company distribution) is categorized as the compound of pigment (Pigment) in, promptly has a compound of Colour Index as described below (C.I.) number.C.I. yellow series pigments such as Pigment Yellow 73 1, C.I. Pigment Yellow 73 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 180, C.I. Pigment Yellow 73 185; C.I. red colour system pigment such as Pigment red 1, C.I. Pigment red 2, C.I. pigment red 3, C.I. Pigment red 177, C.I. Pigment red 254; And C.I. pigment Blue 15, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: blue series pigments such as 6; C.I. green series pigments such as pigment Green 7, C.I. pigment green 36; C.I. pigment Violet 23, C.I. pigment Violet 23: 19 etc.
In addition, can use the high brightness G pigment of the high phthalocyanine of the bromination rate of present difficulties in dispersion, for example phthalocyanine green (monastral green) 6YC, 9YC (manufacturing of ア PVC シ ア Co., Ltd.), the high color purity G pigment that central metal is made of metal, for example Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, different kinds of metals phthalocyanine pigments such as Ge, Sn beyond the copper.
In addition, the concrete example of above-mentioned mineral dye can be enumerated: titanium oxide, barium sulfate, lime carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine, chromoxide green, cobalt green, coral amber Huang, black, the synthetic iron oxide black of titanium, carbon black etc.In the present invention, pigment can use separately or mix more than 2 kinds and use.
Dispersible pigment dispersion can be given excellent dispersiveness with the various pigment of chromatic filter to being generally used for liquid crystal indicator in these pigment, specifically, can be preferred for preparing to contain being selected from by C.I. Pigment Yellow 73 150, C.I. pigment green 36, C.I. pigment Green 7, C.I. pigment yellow 13 8, C.I. pigment yellow 83, C.I. pigment Blue 15: 6, C.I. pigment Violet 23, C.I. Pigment red 177, C.I. Pigment red 254 and C.I. pigment yellow 13 9, the above-mentioned phthalocyanine pigment that the bromination rate is high, the situation of at least a dispersible pigment dispersion in the group that above-mentioned different kinds of metals phthalocyanine pigment constitutes.
Pigment dispersing agent is not particularly limited, and can use various pigment dispersing agents.
As the concrete example of operable pigment dispersing agent, can illustration: pelargonamide, decyl amide, lauramide, N-dodecyl six acid amides, N-octadecyl propionic acid amide, N, N-dimethyl lauramide and N, amide compounds such as N-dihexyl ethanamide; Diethylamine, two heptyl amices, dibutyl hexadecylamine, N, N, N ', amine compound such as N '-tetramethylmethane amine, triethylamine, Tributylamine and trioctylamine; Monoethanolamine MEA BASF, diethanolamine, trolamine, N, N, N ', N '-(four hydroxyethyls)-1, N, N, N '-three (hydroxyethyl)-1,2-diaminoethanes, N, N, N ', N '-four (hydroxyethyl polyoxyethylene)-1,2-diaminoethanes, 1,4-two (2-hydroxyethyl) piperazine and 1-(2-hydroxyethyl) piperazine etc. have the amine of hydroxyl etc., can enumerate compounds such as 3-piperidyl urea, 4-piperidyl urea, niacinamide in addition.
And can enumerate: (being total to) polymer class of esters of unsaturated carboxylic acids such as polyacrylic ester; (part) amine salt of (being total to) polymkeric substance of esters of unsaturated carboxylic acids such as polyacrylic acid, (part) ammonium salt and (part) alkylamine salt; (being total to) polymkeric substance of hydroxyl esters of unsaturated carboxylic acids such as hydroxyl polyacrylic ester and their modifier; Polyurethanes; The unsaturated polyester amides; Polysiloxane-based; Long-chain polyaminoamide phosphate class; By poly-(low-grade alkylidene imines) with contain acid amides that the reaction of free carboxy polyester obtains and their salt.
In addition, as the commercially available product of dispersion agent, can enumerate: シ ゲ ノ Star Network ス-105 (trade(brand)name, Ha ッ コ one Le ケ ミ カ Le company makes), Disperbyk-101, Disperbyk-130, Disperbyk-140, Disperbyk-170, Disperbyk-171, Disperbyk-182, Disperbyk-2001[is above by PVC Star Network ケ ミ one ジ ヤ パ Application (strain) system], EFKA-49, EFKA-4010, EFKA-9009 (above) by the manufacturing of EFKA CHEMICALS company, ソ Le ス パ one ス 12000, ソ Le ス パ one ス 13240, ソ Le ス パ one ス 13940, ソ Le ス パ one ス 17000, ソ Le ス パ one ス 20000, ソ Le ス パ one ス 24000GR, ソ Le ス パ one ス 24000SC, ソ Le ス パ one ス 27000, ソ Le ス パ one ス 28000, ソ Le ス パ one ス 33500[is above by ゼ ネ カ (strain) system], PB821, PB822[is above by monosodium glutamate (strain) system] etc.
Pigment dispersing agent is usually with respect to pigment 100 mass parts to be the ratio use of 10～90 mass parts, preferred 20～80 mass parts.
In coloured composition, further compounding UV blockers as required, UV light absorber, surface conditioner (flow agent) and other compositions.
Coloured composition can be by directly being mixed in (d) composition with (methyl) acrylate composition, pigment, pigment dispersing agent and other compositions as required, use known dispersion machine to make it disperse to make, but colo(u)rant dispersion is insufficient sometimes, therefore, the method that preferably prepares dispersible pigment dispersion in advance.
According to this method, can easily obtain the photosensitive coloring composition of pigment-dispersing excellence.In the method, particularly under the situation of compounding (f) composition, be used for dispersive solvent (below be called " dispersion solvent ") and make its dispersion by pigment, pigment dispersing agent and a part (f) composition as required are mixed in, prepare dispersible pigment dispersion in advance.On the other hand, with its differently by (methyl) acrylate composition and as required (f) composition or other compositions being mixed in the solvent that is used for diluting (below be called " diluting solvent ") and making its dissolving or dispersion, preparation transparent photomask glue.Then, dispersible pigment dispersion and the transparent photomask glue that obtains mixed, carry out dispersion treatment as required, can easily obtain the coloured composition of pigment-dispersing excellence thus.According to this method, owing to can select dispersion solvent and diluting solvent respectively, therefore, the scope that solvent is selected also enlarges.
When not preparing dispersible pigment dispersion in advance, in organic solvent, at first drop into pigment, pigment dispersing agent and alkali soluble resin as required, mix fully, stir and after making colo(u)rant dispersion, append remaining compositions such as containing the carboxyl polyfunctional acrylic ester and mix, thus, not only can be in the dispersing of pigments operation because of other compounding compositions do not influence pigment-dispersing, and stability is also excellent.
The coloured composition that obtains like this is coated on support and form film and make its drying after, by the pattern form irradiation light of this being filmed in accordance with regulations, after a part of filming is optionally solidified, develop with alkali lye, carry out the back baking then, further carry out thermofixation, can obtain the painted of predetermined pattern thus and film.
The preferred ultraviolet ray of light or the visible rays that use use the wavelength light of the 240nm～410nm that is obtained by high pressure mercury vapour lamp or metal halide lamp etc.Solidify the irradiation energy that needs and be generally 10～500mJ/cm 2About.In exposure process,, can make the fixed position of filming optionally expose, solidify by to the surface irradiation laser of filming or across the mask irradiation light.
Developing solution can use the aqueous solution of alkali cpd.Basic cpd for example can be enumerated: potassium hydroxide, sodium hydroxide, yellow soda ash, sodium bicarbonate, water glass, ammonia, Tetramethylammonium hydroxide etc.In addition, in order to promote developing powder, can in developing solution, add water-miscible organic solvent, the various tensio-active agents such as methyl alcohol, ethanol, Virahol and benzylalcohol of appropriate amount.
Developing method can be any of infusion method, pickling process and spray method etc.After the development, washed pattern part with water 0.5～1.5 minute, make it air-dry, obtain colored pattern with pressurized air etc.
In addition, thermofixation by using Vacuumdrier, baking oven, hot plate or other can give the device of heat, is carried out drying usually under 50～200 ℃, then, heat under the temperature about 120～250 ℃, makes its curing.
The cured portion of filming has pigment and is scattered in structure in the matrix equably, and described matrix is that the reticulation of the cross-link bond that forms by photocuring reaction that utilizes the invention described above and thermofixation reaction forms.
The solidified nature excellence of this coloured composition, cross-linking density raise, and to inside all evenly, solidify well, therefore, are not easy to become anti-taper when developing, and can form clear-cut and the good pattern of surface smoothing along cone-shaped.
In addition, coloured composition of the present invention, therefore inclosure impurity in solidifying in the matrix that all the solidified cross-linking density is high well of inside and being not easy in the liquid crystal layer stripping, can obtain the high color solidification film of electric reliability.Particularly when using this coloured composition to make the pigmented layer of liquid crystal panel, can stablize the voltage that keeps display part, electric reliability height.
In addition, above-mentioned coloured composition can make the fine and dispersion equably of pigment of high density, and therefore the tint permanence height, is approaching the also big colored pattern of depth of shade even can form, and the color rendering zone is wide.
Coloured composition can be used to form various painted filming, and particularly is suitable for constituting the pigmented layer of the details of chromatic filter, promptly forms pixel and black matrix.
Since composition of the present invention with (a) composition of alkali-developable excellence and (b) composition be necessary composition, therefore, when using composition as the formation of active energy ray-curable pattern, exposure sensitivity height, development are good, can form precision, pattern accurately, and after curing, various physical properties excellent such as coating strength, thermotolerance and resistance to chemical reagents.
In addition, composition of the present invention is even reduce the compounding ratio of (f) composition, alkali-developable does not reduce yet, therefore, and comparatively speaking, can the compounding of more ground contain as multifunctional (methyl) acrylate of (a) composition of bridging property composition and the ratio of pigment, therefore, also be suitable for forming pigmented layer.
Embodiment
The present invention relates to a kind of active energy ray-curable composition, it is to contain above-mentioned (a) composition and (b) composition is as composition that must composition, and with respect to (a) composition 100 mass parts, preferably the ratio with 0.1～20 mass parts contains (b) composition.
(a) the acid anhydrides affixture of preferred Dipentaerythritol five acrylate of composition.
Composition of the present invention preferably further contains the composition of Photoepolymerizationinitiater initiater, preferably contains the composition of organic solvent in addition.
Composition of the present invention can be used for patterns such as printing ink, coating and photoresist material and form the various uses of using composition, particularly because therefore the alkali-developable excellence, can be preferably used as pattern formation composition.
Pattern forms and preferably further contains alkali soluble resin with composition.
And, form with in the composition at pattern, can be preferably used as coloured composition.
In addition, the present invention relates to a kind of pattern formation method, after described pattern formation method forms in that above-mentioned composition is coated on substrate and films, make its curing across mask irradiation active energy ray from it, utilize developing solution that uncured portion is developed with specific pattern form.
Embodiment
Below, enumerate embodiment and comparative example is described more specifically the present invention.
In addition, following " part " is meant that mass parts, " % " are as long as no specified otherwise is meant quality %.
Zero Production Example 1[(a-1) manufacturing]
In 500 milliliters of glass flasks that have whipping appts, thermometer, water condenser, add propylene glycol monomethyl ether monoacetate [Network ラ レ (strain) system: trade(brand)name PGMAC, below be called " PGMAC "] 110g, contain acrylate mixture (hydroxyl value 36mgKOH/g) 250g of Dipentaerythritol five and six acrylate with 30: 70 (mass ratio), add succinyl oxide 16g, hydroquinone monomethyl ether 0.13g, be warming up to 85 ℃.After wherein dropping into catalyst of triethylamine 1.3g, carry out 3 hours reaction.Be reflected under the mixing atmosphere gas of air/nitrogen and carry out, obtain the compound that acid number is 34mgKOH/g (below be called " ab1 ").
To the compound that obtains, under following condition, utilize high-efficient liquid phase chromatogram technique analysis (a) composition, under following condition, utilize ion chromatography analysis (b) composition, the result is in 100 parts of all acrylates, and (a) composition is 30 parts, and (b) composition is 0.2 part.
● the efficient liquid phase chromatographic analysis condition
Device: East ソ one (strain) system SC-8010
Post: East ソ one (strain) system ODS-100z
Anti-phase (ODS) post (internal diameter 4.6mm, length 250mm).Fill anti-phase (ODS) silicon-dioxide of particle diameter 5 μ m.
Analysis temperature: 40 ℃
Elutriant: 0.015% phosphoric acid water: methyl alcohol (volume ratio)=45: 55 (initially) → 30: 70 (30min) → 0: 100 (45-50min)
The flow velocity of elutriant: 1.0mL/min
Detector: UV 210nm
● ion chromatograph assay determination condition
Device: DIONEX (strain) system DIONEX DX-300
Separator column: DIONEX (strain) makes IonPacAS4A-SC
Guard column: DIONEX (strain) makes IonPacAG4A-SC
Elutriant: 1.8mM-Na 2CO 3/ 1.7mM-NaHCO 3
Flow: 1.5ml/min
Suppressor: ASRS-ULTRA-II (egr mode, current value 50mA)
Detector: specific conductivity
Sample injection rate: 50 μ L
Program: after the dilution with toluene of sample, add the water of 5 times of amounts of sample, after vibrate 10 minutes and leaving standstill, divide and take off layer (water layer), make working sample with 10 times of amounts.
Zero Production Example 2
The add-on of raw material succinyl oxide is set at 20g, in addition, all synthesizes, obtain the compound (below be called " ab2 ") of acid number 50mgKOH/g according to Production Example 1.
The compound and the Production Example 1 that obtain are similarly analyzed, and in 100 parts of all acrylates, (a) composition is 30 parts, and (b) composition is 1.5 parts.
Zero Production Example 3
The add-on of raw material succinyl oxide is set at 13g and will be set at 8 hours the reaction times, in addition, all synthesize, obtain the compound (below be called " ab3 ") of acid number 28mgKOH/g according to Production Example 1.
The compound and the Production Example 1 that obtain are similarly analyzed, and in 100 parts of all acrylates, (a) composition is 25 parts, and (b) composition is 0.015 part.
Zero Production Example 4[(f) manufacturing of composition]
In having the detachable flask of stirrer, thermometer, reflux condensing tube, dropping funnel and nitrogen ingress pipe, add benzyl methacrylate 52%, vinylformic acid 23%, with respect to the monomer total amount be 2 times of amounts PGMAC, with respect to the monomer total amount be 5% 2,2 '-azo two (2-methylbutyronitrile) dissolves it equably.Then, stirring is 2 hours under nitrogen gas stream, under 85 ℃, further makes its reaction 1 hour under 100 ℃.Further in the solution that obtains, add glycidyl methacrylate 25%, be 10% triethylamine, be that to add together weight be 35% DMDG for 1% Resorcinol and the monomer that makes adding and glycidyl methacrylate with respect to glycidyl methacrylate with respect to glycidyl methacrylate, stirred 5 hours the copolymer solution that obtains wanting (solid component concentration 31.5%) down at 100 ℃.
The Mw of (f) composition that obtains (below be called " f1 ") is 21,200, and acid number is 84mgKOH/g, and hydroxyl value is 96mgKOH/g.
Zero embodiment 1～3, comparative example 1～2
With (a)～(c) composition and (e) composition, pigment and pigment dispersing agent mix according to ordinary method, to be the ratio shown in the following table 1, make coloured composition.
The composition that use obtains is according to the method evaluation development same with embodiment 1～3, comparative example 1～2.Residue is estimated according to following method.These be the results are shown in table 1.
＜development 〉
On the wide chromium mask glass substrate of 10cm, utilize in spin coater coating table 1 and 2 composition of record, make this coated film in 80 ℃ blast drier dry 10 minutes, form the coated film of dry film thickness 2 μ m.Filming of obtaining carried out spray development with the 0.5wt% aqueous sodium carbonate, measure to the consoluet time.
＜residue 〉
With containing the cotton rod of alcoholic acid to the substrate surface wiping after the development evaluation 10 times, investigating cotton rod has non-coloring, estimates with following standard.
Zero: cotton rod does not have painted fully.
△: cotton rod is painted a little.
*: cotton rod is painted.
[table 1]
The numeral on composition one hurdle in the table 1 is meant part, and ab1～ab3 and f1 represent as the solids component ratio.
In addition, the abbreviated expression in the table 1 is as described below.
Irg907:2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholino propane-1-ketone, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ company make イ Le ガ キ ユ ア 907
M-402: Dipentaerythritol five acrylate/dipentaerythritol acrylate mixture (ratio: about 30/70) East Asia synthetic (strain) system ア ロ ニ ッ Network ス M-402
PB: pigment, C.I. pigment Blue 15: 6
DIS: pigment dispersing agent, Disperbyk-2001, solid formation are divided 46% (main solvent: acetate methoxyl group propyl ester, methoxypropanol, ethylene glycol butyl ether)
(a) contained in the composition of his-and-hers watches 1 reaches (b) composition, is summarized in following table 2.
[table 2]
Numeral in the hurdle of table 2 is meant part.
* " (b) ratio ": be meant the ratio of (b) composition with respect to 100 parts of (a) compositions.
The composition of embodiment 1～3, development are very excellent, have not a particle of youngster's residue on the substrate.
With respect to this, (b) components in proportions is lower than 0.1 part comparative example 1, and its development, residue are all poor slightly as a result.In addition, using commercially available multifunctional (methyl) acrylate and do not containing in the comparative example 2 of (b) composition, development, residue are also all insufficient.
Composition of the present invention can be used for various uses such as printing ink, coating and photoresist material, can be preferably used as pattern formation compositions such as photoresist material.
And composition of the present invention can be preferably used as the coloured composition of the pixel that is used to form the chromatic filter of liquid crystal panel in making and black matrix etc.

Claims (8)

1. active energy ray-curable composition, its be contain compound (a) and
The composition of the necessary composition of the hydrolyzate of acid anhydrides or acid anhydrides (b) conduct,
Described compound (a) is that the addition acid anhydrides forms on the compound with (methyl) acryl and hydroxyl more than 3, with respect to (a) composition 100 mass parts, contains (b) composition with the ratio of 0.1～20 mass parts.
2. active energy ray-curable composition as claimed in claim 1, wherein, above-mentioned (a) composition is the acid anhydrides affixture of Dipentaerythritol five acrylate.
3. as claim 1 or the described active energy ray-curable composition of claim 2, it also contains Photoepolymerizationinitiater initiater and forms.
4. as each described active energy ray-curable composition in claim 1～claim 3, it also contains organic solvent and forms.
5. an active energy ray-curable pattern forms and uses composition, and it comprises each described composition in claim 1～claim 4.
6. active energy ray-curable pattern as claimed in claim 5 forms and uses composition, and it also contains alkali soluble resin and forms.
7. an active energy ray-curable pattern forms and uses coloured composition, and it comprises claim 5 or the described composition of claim 6.
8. pattern formation method, its each described composition in claim 5～claim 7 be coated on substrate and form film after, make its curing across mask irradiation active energy ray from it, utilize developing solution that uncured portion is developed with specific pattern form.
CNA2006800370958A 2005-10-07 2006-10-05 Composition curable with actinic energy ray Pending CN101283005A (en)

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CN106444287A (en) * 2016-09-28 2017-02-22 江苏博砚电子科技有限公司 Acrylate resin for colored photoresist and preparation method of acrylate resin
CN106444287B (en) * 2016-09-28 2019-07-16 江苏博砚电子科技有限公司 A kind of chromatic photoresist acrylate and preparation method thereof
CN110582709A (en) * 2017-05-11 2019-12-17 日本化药株式会社 Ultraviolet-curable resin composition for blue light-filtering film and blue light-filtering film using same
CN114894953A (en) * 2022-05-09 2022-08-12 广州谱临晟科技有限公司 Method for detecting organic acid in environment

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JPS5931947A (en) * 1982-08-17 1984-02-21 Mitsui Toatsu Chem Inc Composition for forming pattern hardenable with ultraviolet rays
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CN102591153A (en) * 2012-02-21 2012-07-18 绵阳信利电子有限公司 Light-sensitive resin as well as preparation method and application thereof
CN106444287A (en) * 2016-09-28 2017-02-22 江苏博砚电子科技有限公司 Acrylate resin for colored photoresist and preparation method of acrylate resin
CN106444287B (en) * 2016-09-28 2019-07-16 江苏博砚电子科技有限公司 A kind of chromatic photoresist acrylate and preparation method thereof
CN110582709A (en) * 2017-05-11 2019-12-17 日本化药株式会社 Ultraviolet-curable resin composition for blue light-filtering film and blue light-filtering film using same
CN114894953A (en) * 2022-05-09 2022-08-12 广州谱临晟科技有限公司 Method for detecting organic acid in environment

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KR20080064120A (en) 2008-07-08

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